Sulfamyl couplers in mixed packet photographic emulsions



Unite ates iiee

' SULFAMYL COUPLERS IN MIXED IPAQKET PHUTOGRAPHEC EMULSHN 1 ob ects will appear from the following description of our invention.

These objects are accomplished by incorporatin a particular type of coupler in a colloid-silver halide em 1- 5 sion in the presence of a Water-soluble salt of a polymer z containing salt forming acid'groups e. g. a methylmeth- Homer W. 15. Cressman and scheming S. Fierlre, Rochacrylate methacryfic acid copolymr, bringing the PH ester, N. Y., assignors to Eastman Kodak (Company, f th l t b 7 t 1 ft Rochester N Y a corporation of New Jersey 0 e um 10 Pom lmme la-ey a er 7 adding the polymer, and adding a packet-forming com- No Drawing Appfimfiou Mamh 26, 1953 10 ponent, e g. a styrene-maleamic acid copolymer, to gamma N00 344 894 rorm particles of colloid packet-forming component and silver halide, containing the coupler. 6 Ciairns. (Ci. %'--2) The couplers which we propose to use are couplers or color forming compounds capable of reacting with the This invention relates to color photography and par- 9X1dat10fi Product Of a P 1 3 al'omatlc arming P P' ticularly to mixed packet photographic emulsions. mg agent 5 p s ph development, contamms p The h b many prior suggestions f ixed or more or the following groups: sulfamylbenzamido, grain photographic emulsions, that is, photographic sysd1-S1l1famy1b@nZa m1d0, alkylsullamylbfinmmldo, f yltems in which differently sensitized silver halide grains sulfamylbepzamldo, am1110allgylsuifarpylbenzamldo, are incorporated in a single photographic emulsion layer 2 H1111 9 alliylsllpliamylbelliElmldo, hyuroxyalkylsulfamyland used to produce diiferently colored photographic bellZamldO, Giny@mXYEliiylsulfamylbenzfirmdu images in the layer. Mixed grain systems have a num- These Couplers have the general Structure: ber of advantages, chief among which is the simplicity R! of coating a single emulsion layer rather than several layers. Other advantages are the improved definition K obtained by having the differently sensitized particles R2 juxtaposed in a single layer, and the simplification of processing which is generally obtained. 1 p It is sometimes advantageous to incorporate color X forming compounds or couplers of the water-soluble type where either in multilayer or mixed packet emulsions. Such Z:a Coupler couplers should be non-diffusing, particularly 1n m xed R1, gzzhydl-ogen, m 1 aminoalkyl or hydroxyalkyl, packet emulsions, but should possess sufiicient reactivity hydroxyethyl int the color forming reaction to yield adequate dye den- X:h d or s1 res. R1

It is therefore an object of the present invention to so provide a novel incorporated coupler emulsion. A fur- 2 ther object is to provide a method of incorporating cou- R2 plers in silver halide emulsions. A still further object The following couplers are suitable for use according is to provide a novel mixed packet emulsion. Other 40 to our invention:

( SO2NHCH2CH2OH 0H NHOO- coNHoHioHi-N11oo domnornomon C C5Hn 1 hydroxy- 4 chloro N {4 [2"- (2"',4"'- di tert amylphenoxy) 5- (3.5- di B hytlr0xyethylsulfamylbenzamide) benzamido] phene thyl}-2-naphthamide. (2) SO2N(CHzCH2OH)a OH NHCO- AO2N(CH2CHZOH)2 phenoxy) 5"- yl) ]}benzamidol phenethyl}-2-naphtharnide,

NHO O- CsHu a (o methoxybenzoyl) 4 {2- [2,4 di tert amylpheno y] 5'- i3 (B mido}acetanilide.

The silver halide emulsions in which these couplers are incorporated may be optically sensitized and ordinarily two or more emulsions sensitive to difierent regions of the visible spectrum will be employed and mixed.

The coupler may be made in dispersion in gelatin or in solution in Water, added to the silver halide emulsion or to the water-soluble salt such as the salt of methylmethacrylate-methacrylic acid copolymer, and then the remaining component that is, either the Water-soluble salt or the silver halide emulsion, added to the-mixture.

The water-soluble salt of the polymeric material containing salt-forming acid groups which isemployed in forming the emulsion may be a salt obtained from the copolymer of methacrylic acid and methyl-a-methacrylate (Minsk, Weyerts and McDowell U. S. Patent 2,391,181), algin (alkali metal salt of polymeric-d-mannuronic acid), carboxymethyl cellulose (Collins, Freeman and Anthonisen U. S. Patent 2,278,612), or cellulose sulfate (Belgian Patent 448,249). The water-soluble polymer when mixed with the gelatin of the dispersion acts as a modifying agent so that small packets containing appropriately sensitized silver halide and colorforming coupler can be formed.

The polymeric packet-forming component consists of a polymeric carbon chain having recurring phenyl groups and carboxylic acid groups and preferably also carboxylic acid amide groups or imide groups or both and is used as the water-soluble salt such as the ammonium, sodium, potassium or lithium salt. T hepolymeric packet-forming component is preferably an interpolymer of styrene and an a,B-unsaturated carboxylic acid, part of whose carboxyl groups may have been converted to amide or imide derivatives or both, such as interpolymers of styrenemaleic acid, styrene-acrylic acid, styrene-methacrylic acid, or styrene-itaconic acid.

The packet emulsion in its single layer or single color form consists of particles or packets of gelatin associated With polymeric packet-forming component containing silver halide and coupler, the packets being dispersed in an aqueous medium containing additional gelatin or another film-forming water-soluble polymer. To make a mixed packet emulsion this single emulsion is mixed with at least one other similarly made packet dispersion containing differently sensitized silver halide and different coupler to form the finished mixed packet emulsion.

In the preparation of the system described above, that is, gelatin, water-soluble polymer, and packet-formmg component, the ingredients must be present in a hydroxyethylsulfamyl benzamido benzafairly definite ratio. If the gelatin is present in approximately 0.7% aqueous solution (an appropriate concentration for making an emulsion), then the Watersoluble polymer should be present in an amount from about 1 to 2 times that of the gelatin, and the packet forming component should be present in an amount from 0.01 to 0.5 times that of the gelatin. Within these ranges the three-component systems exhibit a definite degree of optical turbidity. If this turbidity 1s measured in optical density per cm. of mixture at 30 C., us ng orange-colored light, of about 5800 A. U., the optlcal density is greater than 0.05, and is generally of the order of 0.1.

Suitable polymers of styrene with maleic acid or its derivatives which may be used as the polymeric packetforrning component according to our invention are described in Godowsky U. S. application Serial No. 156,066, filed April 15, 1950. The polymers illustrated in Examples 2 and 3 of the Godowsky application are especially suitable for use according to our invention.

The hydroxyalkyl sulfamyl couplers which we use were prepared in general by treating the parent coupler containing a chlorinated sulfonic acid group or groups with the appropriate amine. The preparation 1s described in detail in Salminen and Weissberger U. S. application Serial No. 344,884, filed concurrently herewith.

The following two examples describe preparation of the coupler dispersions in gelatin.

Example 1.Dispersi0n in gelatin 0 Compound 1 An intimate mixture of 9.92 g. of l-hydroxy-4-chloro- N {4' [2" (2"',4 di tert amyl) phenoxy 5"- (3',5" dichlorosulfonyl)benzamido] benzamido} phenamyl-Z-naphthamide, 20.0 cc. of methanol, and 4.0 cc. of monoethanolamine, after the first vigorous exothermic reaction had subsided, was heated to 55 C. The clear solution, after 15 minutes at 55 C., was poured slowly into a mechanically agitated solution of 75.0 g. of a 10% deashed gelatin solution, and 5 cc. of a 5% Alkanol B solution. The mixture was milled 5 times through a colloid mill, chilled. shredded, and washed in 5 changes of 800 cc.

- of water; the first and second portions contained respectively 8 cc. and 5 cc. of a 20% acetic acid solution to take out excess ethanolamine. The washed noodles and 5 cc. of a 5% Alkanol B solution were stirred for 30 minutes at 40 C. and finally passedfive times through the colloid mill set at .010". The weight of the coupler dispersion was ,g.

Example 2.Dispersion in gelatin of Compound 14 A mixture of 4.73 g. of 1-phenyl-3-{3-[2-(2",4"- di tert amylphenoxy) (3"',5' dichlorosulfonyl) benzamido] benzamido} benzamido 5 pyrazolone, 20 cc. of methanol, and 5 cc. of monoethanolamine was heated to 55 C. and maintained at that temperature for minutes. The dark brown solution was then slowly poured into 1000 cc. of cold tap Water, vigorously agitated. The colloidal precipitate, after acidification (pH 6.5) of the aqueous mixture, was collected on a Buchner funnel, washed a second time by stirring in 500 cc. of distilled water, was sucked as dry as possible on the filter. It was then stirred into 25.0 g. of a deashed 10% gelatin solution, 25 cc. distilled water, and 5 cc. of a 5% Alkanol B solution. The coupler-gelatin mixture was passed five times through the colloid mill set at .010". The weight of the dispersion was 95.0 g.

Packet emulsions were prepared from the coupler dispersions in gelatin as follows:

Example 3 A mixture of 21.3 g. of the coupler dispersion described in Example 1, 39.6 g. of a red-sensitive emulsion, (containing permole of silver halide 80.0 g. of gelatin in a total weight of 1320 g.), and 25.0 cc. of distilled water was stirred at 40 C. for 5 minutes. The above components had been preheated to 40 C. prior to mixing. To this well-stirred, intimate mixture was then added 70.0 g. of a 10% solution of a copolymer of methyl methacrylate and methacrylic acid. The pH of this mixture, after stirring for 5 minutes at 40 C., was adjusted to 6.6 by slowly adding 5 cc. of a 10% citric acid solution. After the addition of 5.0 cc. of a 5% Alkanol B solution, the above mixture was moderately stirred at 40 C. for 20 minutes. To this intimate mixture was then added all at once 29.0 cc. of a 1% solution of styrenemaleamic acid copolymer, preheated to 40 C. The Whole was vigorously stirred for 5 minutes and moderately stirred for another 18-20 minutes, then the packet reaction was complete. The well-defined particles averaged approximately 5a in size. There was no freesilver halide in the matrix on testing by microscopic examination a portion of the reaction mixture in a 5% gelatin solution.

The cyan packet emulsion prepared in this manner, after the addition of 75 cc. of 10% deashed gelatin solution and 5 cc. .of a 7.5% saponin solution, weighed 275.0 g.

Example 4 A magenta packet emulsion was prepared similarly to Example 3, from 21.2 g. of the coupler dispersion described under Example 2, 27.6 g. of a green-sensitive emulsion (1370 g. per mole of silver halide and 80 g. of

gelatin), 30 cc. of water, 48 cc. of a 10% solution of Example 5 A mixture of 20.0 g. of Compound 1, 30.0 cc. of methanol, and 2.0 cc. of a 20% aqueous sodium hydroxide solution was stirred at 60 C. for 5 minutes. To this almost clear solution was then added 48.0 cc. of water, and the whole stirred at 55-60 C. for another minutes. The coupler solution (100 cc.) was filtered and 90.0 cc. of the filtrate, containing 18.0 g. of the cyan coupler No. 1, was added with efficient mechanical stirring to 204.0 g. of a 9.8% solution of a copolymer of methyl methacrylate and methacrylic acid (40 C.). To this mixture, after stirring for a minute or two at 40 C., was added slowly 22.8 cc. of a 10% citric acid solution and then stirred for 10 minutes. To this mixture was added 79.2 g. of a red-sensitive emulsion, (containing per mole of silver halide 80 g. of gelatin in a total weight of 1320 g.), 40.0 cc. of water and 6.0 cc. of a 5% Alkanol B solution. Into this mixture, after stirring at 40 C. for 30 minutes, was poured from a graduate 48.0 cc. of a 1% solution of a styrene-maleamic acid copolymer, preheated to 40 C. The whole was vigorously stirred "12 for the first 5 minutes and then moderately for another 25 minutes. A 10% solution of a deashed gelatin (180.0

.cc.) .and 20 cc. of a 7.5% saponin solution were then added.

The cyan packet emulsion prepared in this manner weighed 685 g. 'The average particle size was 5 to 8a with a few clumps as high as 15;/..

Example 6 Ama'genta coupler solution was prepared from 18.0 g. of Compound 14, 30.0 cc. of methanol, 30 cc. of a 20% sodium hydroxide solution, and 149.0 cc. of water.

The magenta packet emulsion was prepared according to the procedure described in detail under Example 5. The various components used were:

The total weight of the magenta packet emulsion prepared in this manner amounted to 800.0 g.

A two-color mixed packet emulsion was made as follows: Example 7.The mixed emulsion was made by mixing the following ingredients in the order stated:

33.0 g. of cyan emulsion (Ex. 3) 14.0 g. of magenta emulsion (Ex. 4)

0.378 g. of dioctyl hydroquinone dissolved in dibutyl phthalate and dispersed in gelatin 0.0043 g. of benzothiazole methiodide in 2.6 ml. of

methanol 0.8 cc. of a 20% 'KCl, 2% KBr solution 1.0 cc. of .a 7.5 saponin solution .008 g. of mucochloric acid in 0.3 cc. of water 60.0 g. total The red and green exposed areas of these plates on processing in a primary aromatic amino color developing solution yielded respectively cyan and magenta dye images of satisfactory color density. The color separation was quite good.

Numerous modifications may be made in the packet systems within the scope of our invention. in a multilayer film one or more couplers may be incorporated in packets and the remaining coupler or couplers may be incorporated in separate layers in dispersion in a coupler solvent or directly incorporated in the gelatin of the emulsion. In a mixed system two packets of difierent couplers may be incorporated in a single gelatin layer and a third coupler incorporated in another layer either directly in the emulsion or in dispersion in a solvent for the coupler. In a single emulsion layer, all three couplers may be in packets and the third coupler incorporated in a surrounding silver halide emulsion in the same layer. Antistain agents other than dioctylhydroquinone may be used in the emulsion such as diamylhydroquinone and didodecylhydroquinone.

It will be understood that the examples and modifications included herein are illustrative only and that the invention is to be taken as limited only by the scope of the appended claims.

We claim:

1. The method of making a packet photographic emulsion which comprises forming a mixture of (1) a nondiflusing color-forming compound capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development and con taining 21 group selected from the class consisting of sulfamylbenzamido, disulfamylbenzamido, alkylsulfamylbenzamido, dialkylsulfamylbenzamido, aminoalkylsulfamylbenzamido, diaminoalkylsulfamylbenzarnido, hydroxyalkylsulfamylbenzamido, dihydroxyalkylsulfamylbenzamido, phenylalkylsulfamylbenzamido, and diphenylalkylsulfamylbenzamido groups, (2) a gelatino-silver halide emulsion and (3) a water-soluble salt of a polymer selected from the class consisting of methacrylic acidmethyl-a-methacrylate copolymer, algin, carboxymethyl cellulose and cellulose sulfate, said coupler being added to one of said other ingredients before the third ingredient is added, bringing the pH of the mixture below 7 immediately after adding said water-soluble salt, and adding to the mixture with stirring a solution of a polymeric carbon chain compound having recurring phenyl groups, carboxylic acid groups and amide groups to form a dispersion of particles of gelatin, packet-forming component and silver halide, containing said color-forming compound.

2. The method of making a packet photographic emulsion which comprises forming a mixture of (l) a nondifiusing coupler compound containing a hydroxyalkylsulfarnylbenzamido group and capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, (2) a gelatino-silver halide emulsion and (3) a water-soluble salt of a copolymer of methacrylic acid and methyl-umethacrylate, said coupler being added to one of said other ingredients before the third ingredient is added, bring the pH of the mixture below 7 immediately after adding said water-soluble salt, and adding to the mixture with stirring a solution of a water-soluble salt of an interpolymer of styrene and an O S-unsaturated carboxylic acid to form a dispersion of particles of gelatin, salt of said interpolymer and silver halide, containing said colorforming compound.

3. The method of making a packet photographic emulsion which comprises dispersing in gelatin a non-diffusing coupler compound containing a hydroxyalkylsulfarnylbenzamido group and capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, mixing said coupler dispersion with a gelatino-silver halide emulsion, mixing with the emulsion and coupler mixture a solution of a water-soluble salt of a copolymer of methacrylic acid and methylwt-methacrylate, bringing the pH of the resulting mixture below 7, and then adding to the mixture with stirring a solution of a water-soluble salt of an interpolymer of styrene and an a,,B-l.1l1Satl11'atCd carboxylic acid to form a dispersion of particles of gelatin, salt of said interpolymer and silver halide, containing said coupler compound.

4. The method of making a mixed packet photographic emulsion which comprises dispersing in gelatin a nondiifusing coupler compound containing a hydroxyalkylsulfamylbenzamido group and capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development, mixing said coupler dispersion with a gelatino-silver halide emulsion sensitive to one region but less than all regions of the visible spectrum, mixing with the emulsion and coupler mixture a solution of a water-soluble salt of a copolymer of methacrylic acid and methyl-a-methacrylate, bringing the pH of the resulting mixture below 7, and then adding to the m xture with stirring a solution of the ammonium salt of styrene-maleic acid anhydride copolymer to form a dispersion of particles of gelatin, ammonium salt of said copolymer and silver halide, containing said coupler compound, and forming in the same way as said lastmentioned dispersion at least one other dispersion of particles of gelatin, styrene-maleic acid anhydride copolymer, silver halide sensitive to a difierent region of the visible spectrum than said first-mentioned silver halide, and a non-diffusing coupler compound containing a hydroxyalkylsulfamylbenzamido group and capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development different from said first-mentioned coupler compound, and mixing said dispersions of particles together.

5. The method of making a packet photographic emulsion which comprises mixing with a solution of a nondiiiusing color-forming compound containing a hydroxyalylsulfamylbenzamido group and capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development a solution of a water-soluble salt of a copolymer of methacrylic acid and methyl-ot-methacrylate, bringing the pH of the resulting solution below 7, mixing with the solution a gelatinosilver halide emulsion, and then adding to the resulting mixture with stirring a solution of a water-soluble salt of an interpolymer of styrene and an cap-unsaturated carboxylic acid to form a dispersion of particles of gelatin, salt of said interpolymer and silver halide, containing said color-forming compound.

6. The method of making a mixed packet photographic emulsion which comprises dispersing in gelatin a nondifiusing color-forming compound containing a hydroxyalkylsulfamylbenzamido group and capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development a solution of a water-soluble salt of a copolymer of methacrylic acid and methyl-a-methacrylate, bringing the pH of the resulting solution below 7, mixing with the solution a gelatino-silver halide emulsion sensitive to one region but less than all regions of the visible spectrum, and then adding to the resulting mixture with stirring a solution of the ammonium salt of styrene-maleic acid anhydride copolymer to form a dispersion of particles of gelatin, salt of said copolymer and silver halide, containing said color-forming compound, and forming in the same way as said last-mentioned dispersion at least one other dispersion of particles of gelatin, styrene-maleic acid anhydride copolymer, silver halide sensitive to a different region of the visible spectrum than said first-mentioned silver halide, and a non-diffusing color-forming compound containing a hydroxyalkylsulfamylbenzamido group and capable of reacting with the oxidation product of a primary aromatic amino developing agent on photographic development diiferent from said first-mentioned color-forming compound, and mixing said dispersions of particles together.

References Cited in the file of this patent FOREIGN PATENTS 878,094 France Sept. 28, 1942 

1. THE METHOD OF MAKING A PACKET OF PHOTOGRAPHIC EMULSION WHICH COMPRISES FORMING A MIXTURE OF (1) A NONDIFFUSING COLOR-FORMING COMPOUND CAPABLE OF REACTING WITH THE OXIDATION PRODUCT OF PRIMARY AROMATIC AMINO DEVELOPING AGENT ON PHOTOGRAPHIC DEVELOPMENT AND CONTAINING A GROUP SELECTED FROM THE CLASS CONSISTING OF SULFAMYLBENZAMIDO, DISULFAMYLBENZAMIDO, ALKYLSULFAMYLBENZAMIDO, DIALKYLSULFAMYLBENZAMIDO, AMINOALKYLSULFAMYLBENZAMIDO, DIAMINOALKYLSULFAMYLBENZAMIDO, HYDROXYALKYLSULFAMYLBENZAMIDO, DIHYDROXYALKYLSULFAMYLBENZAMIDO, PHENYLALKYLSULFAMYLBENZAMIDO, AND DIPHENYLALKYLSULFAMYLBENZAMIDO GROUPS, (2) A GELATINO-SILVER HALIDE EMULSION AND (3) A WATER SALT OF A POLYMER SELECTED FROM THE CLASS CONSISTING OF METHACRYLIC ACIDMETHYL-A-METHACRYLATE COPOLYMER, ALGIN, CARBOXYMETHYL CELLULOSE AND CELLULOSE SULFATE, SAID COUPLER BEING ADDED TO ONE OF SAID OTHER INGREDIENTS BEFORE THE THIRD INGREDIENT IS ADDED BRINGING THE PH OF THE MIXTURE BELOW 7 IMMEDIATELY AFTER ADDING SAID WATER-SOLUBLE SALT, AND ADDING TO THE MIXTURE WITH STIRRING A SOLUTION OF A POLYMERIC CARBON CHAIN COMPOUND HAVING RECURRING PHENYL GROUPS, CARBOXYLIC ACID GROUPS AND AMIDE GROUPS TO FORM A DISPERSION OF PARTICLES OF GELATIN, PACKET-FORMING COMPONENT AND SILVER HALIDE, CONTAINING SAID COLOR-FORMING COMPOUND. 